Method of controlling fungi in plants and seeds using ortho-substituted benzoates and thiobenzoates

ABSTRACT

A process for protecting objects against fungi attack by treating the objects with a fungitoxic amount of a substituted benzoic ester.

United States Patent Osieka et al.

METHOD OF CONTROLLING FUNGI IN PLANTS AND SEEDS USINGORTI-IO-SUBSTITUTED BENZOATES AND THIOBENZOATES Inventors: Hans Osieka,Ludwigshafen; Karl- I'Ieinz Koenig, Frankenthai; Ernst- IIeinrichPommer, Limburgerhof, all

of Germany Assignee: Badische-Anilin- & Soda-Fabrik Aktiengese il schaft, Ludwigshafen/R- hine, Germany Filed: Sept. 17, 1969 Appl. No.:858,838

Foreign Application Priority Data Sept. 24, 1968 Germany ..P 17 93 480.4

U.S. Cl. ..424/308, 424/309, 424/357 Int. Cl. ..A0ln 9/20, AOln 9/12Field of Search ..424/308, 309

[ Jan. 16, 1973 OTHER PUBLICATIONS C. Haerdtl Chem. Abs. 1964, V01. 60,pp. 8,374 and 8,375

Primary ExaminerAlbert T. Meyers Assistant Examiner-Dale R. Ore

Attorney--Johnston, Root, OKeeffe, Keil, Thompson & Shurtleff [57]ABSTRACT A process for protecting objects against fungi attack bytreating the objects with a fungitoxic amount of a substituted benzoicester.

3 Claims, No Drawings METHOD OF CONTROLLING FUNGI IN PLANTS AND SEEDSUSING ORTHO-SUBSTITUTED BENZOATES AND THIOBENZOATES The presentinvention relates to fungicides containing substituted benzoic acids asactive ingredients.

It is known to use tetramethylthiuram disulfide for controlling fungi;however, its action is not always satisfactory.

We have now found that compounds having the formula where R denotes alower alkyl radial (methyl, ethyl, propyl, isopropyl, butyl, sec-butyl,isobutyl, tert-butyl), halogen (preferably chlorine, bromine, iodine), a

trifluoromethyl, nitro, amino, alkylamino (methylamino, ethylamino,propylamino, butylamino), dialkylamino (dimethylamino, diethylamino,

dipropylamino), carboxy, acylamino (formylamino, acetyl, propionyl,butyryl, valeryl), alkoxycarbonyl (methoxycarbonyl, ethoxy, propoxy),aryloxycarbonyl (phenoxycarbonyl), thiocyano, mercapto, cyano,hydroxymethyl, chloromethyl, cyanomethyl or an alkoxy radical (methoxy,ethoxy),

R has the same meanings as R but does not mean chlorine, R and R beingidentical or different,

n denotes one of the integers 0, l and 2 and if n denotes 2, the two Rsubstituents may be identical or different,

R denotes a linear or branched alkyl radical (one to 18 carbon atoms)which may be substituted by halogen (preferably chlorine and bromine),alkoxy (methoxy, ethoxy, propoxy, isopropoxy, butyloxy, isobutyloxy,sec-butyloxy, pentyloxy, hexyloxy), chloroalkoxy (chloroethyloxy),alkylthio (methylthio, ethylthio, propylthio, butylthio), alkenylthio(allylthio), alkylsulfonyl (methylsulfonyl, ethylsulfonyl,propylsulfonyl, butylsulfonyl), alkylsulfynyl (methylsulfynyl,ethylsulfynyl, propylsulfynyl, butylsulfynyl), cyano, monoalkylamino ordialkylamino (methylamino to butylamino, dimethylamino) or mercapto, theradical Z denoting oxygen or a nitrogen atom which may be substituted bya lower alkyl group (methyl, ethyl), an alkenyl or alkynyl radicalhaving three to six carbon atoms (alkyl, buten-2-yl-l, methallyl,2-methylbuten-lyl-4, propargyl, butyn-l-yl-3, 3-methylbutyn-l-yl-3, 3-methylpentyn-l-yl3), a cycloalkyl radical or a polycycloalkyl (up totetracyclo) radical (bicyclo-[2,2,l] heptyl radical, cyclohexyl radical,tetrahydrodicyclopentadienyl radical, tetracyclo- [6,2,1 ,1 dodecylradical), a phenyl radical, the benzyl radical, a phenyl radical whichmay be substituted up to three times by alkyl (one to nine carbon atoms,methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl,sec-ethyl, isooctyl, isononyl), up to five times by halogen (preferablychlorine), up to twice by nitro, amino, monoalkylamino or dialkylamino(methylamino, allylamino, dimethylamino, diethylamino acylamino(acetylamino,

R denoting a lower alkyl radical having up to five carbon atoms (methyl,ethyl, propyl, isopropyl, butyl), the radical R and R denoting hydrogenor lower alkyl radicals having up to five carbon atoms (methyl, ethyl,propyl, butyl, isobutyl, amyl), or the radical R denoting a lower alkylradical having up to five carbon atoms (methyl, ethyl, propyl, butyl,amyl) or a phenyl radical,

and X and Y denote oxygen or sulfur,

have a good action on injurious fungi, particularly on those belongingto the basidiomycetes class, e.g. Rhizactonia solani, Coniophoracerebella, Sclerotium rolfsii, Tilletia tritici). The active ingredientsare suitable' for'protecting plants, seeds and seedlings against fungusattack.

The active ingredients according to the invention may be prepared insimple manner, e.g. by reacting the corresponding substituted benzoichalides with the corresponding alcohols or thioalcohols or phenols.Their preparation is illustrated by way of the following examples.

Production of thiomethyl 2,3-dimethylbenzoate 16.8 parts by weight of2,3-dimethylbenzoic chloride is dripped, at 5C, into a solution of 5parts by weight of methyl mercaptan in 50 parts by weight of dioxane, inthe presence of 10.1 parts by weight of triethylamine, and the wholesubsequently heated at 60C. After 3 hours, the triethylaminehydrochloride formed is separated by suction filtration, the filtrate iswashed with ether and dilute hydrochloric acid, the ether phase iswashed twice with water and dried over calcium chloride, and thesolvents subsequently evaporated off in vacuo. Thiomethyl2,3-dimethylbenzoate is obtained by distillation in yield of percent ofthe theory; hp. (0.4 mm) 96 to 97C; n 1.5735.

15.5 parts by weight of o-methylbenzoic chloride is dripped at roomtemperature into a solution of 7.4 parts by weight of isobutanol and10.1 parts by weight of triethylamine in 100 parts by weight of dioxaneand the whole subsequently stirred for 3 hours at 60C. The hydrochlorideformed is separated by suction filtration, ether and dilute hydrochloricacid are added to the filtrate, the ether phase is dried over sodiumsulfate after washing twice with water, and the residue, afterconcentrating the solution in vacuo at 40C, is purified by distillation.

Yield: 93 percent of the theory; b.p.(0.l mm) 71C; n,, 1.4980.

Production of thiooctyl o-chlorobenzoate Production of2'-isopropyl-5-methylpheny1 2- methylbenzoate 15.0 parts by weight of2-isopropyl-5-methylphenol and 10.1 parts by weight of triethylamine in100 parts by weight of dioxane are placed in a vessel, 15.5 parts byweight of o-methylbenzoic chloride is added at room temperature and thewhole subsequently kept for 3 hours at 60C. Distillation is carried outafter the isolation procedure as described above.

Yield: 85 percent of the theory; b.p. (0.2 mm); 135C; n 1.5496.

Examples of other active ingredients which may be prepared by the abovemethods are as follows:

methyl-Z-nitrobenzoate b.p.(l mm) 122 to 124C,

n,,*=1.5338 3'-methylphenyl-Z-chlorobenzoate b.p.(0.1 mm) 138C to 140C,

n,,= 1.5768 thioisopropyl-2-nitrobenzoate b.p.(0.l mm) 126 to 128C,

n,,"=1.5625 propyl-Z-nitrobenzoate b.p.(23 mm)l75 to 177C,

thiomethyl2-chloro-5- nitrobenzoate m.p.72 to 74Cphenyl-Z-methylbenzoate thiophenyl-2-chlorobenzoateisobutyl-2-chlorobenzoate isobutyl-Z-nitrobenzoate thioethyl-2-chlorobenzoate thioisopropyl 2-chlorobenzoate methyl-2-methylbenzoatethiomethyl-Lmethylbenzoate thiomethyl-2-chlorobenzoatethiomethyl-2-nitrobenzoate ethyl-2-methylbenzoatepropyl-Z-methylbenzoate thioethyl-Z-chlorobenzoate b.p.(0.l mm)8 lto83C, n,,"=

1.5740 b.p.( l8mm)l 16C, n 1.5012

isopropyl-Z-methylbenzoatc allyl-2-methylbcnzoatc n,,"=1.5190thiododecyl-2-chlorobenzoate b.p.(O. 1mm l 47to 151C,

n =l .53 10 thiooctyl-Z-nitrobenzoate b.p.(O. 1mm) 166to 168C,

2', 3', 4', 5', 6'-pentachloro phenyl-Zmitrobenzoate4'-isooctylpheny1-2- methylbenzoate methyl-Z-aminobenzoate m.p.l88C to189C m.p. 69 to 70C b.p. (15 mm) 135.5C, n,,"=

The fungicides according to this invention may be 5 water or organicsolvents by means of wetting or dispersing agents. Concentrates whichare suitable for dilution with water may be prepared from activeingredient, emulsifying or dispersing agent and possibly solvent.

Dusts may be prepared by mixing or grinding the ac tive ingredients witha solidcarrier.

The following comparative experiments demonstrate the superiorfungicidal properties of the compositions according to this inventionover known active ingredients.

EXAMPLE 1 The active ingredients were dissolved in acetone in amounts of0.025 and 0.01 percent by weight and uniformly distributed in a stillliquid malt nutrient agar..

The agar was poured into Petri dishes having a diameter of 5 cm. Aftersolidification of the agar, the dishes were centrally inoculated withmycelium flakes of Rhizoctonia solani. The dishes were incubated at 25Cand the extent of the development of the fungus colony ascertained after4 days.

The figures in the table have the following meanings:

0 no fungus growth 1 diameter of the fungus colony of 0.5 to 1 cm 2diameter of the fungus colony of l to 2 cm 1 3 diameter of the funguscolony of2 to 2.5 cm

4 diameter ofthe fungus colony of 2.5 to 4.5 cm

5 diameter of the fungus colony of 4.5 to 5 cm khizoclrmia sulanipercentage active ingredient in the Rhizoctonia aolani percentage activeingredient in the agar Active ingredient 0.025 0.01

/CH; C O OCH /CH; --C O SCH C O SC2H5 C O O--C;H

-CO O-C3H7 /CHa OOSCH ()0 S''CIIJ (l()()"-()Hr* S 0 l A U H:

Ulla

(I11; (I 0 'CH.1

-C 0 S -CII3 I 0 l N- -(JOS-G1I 'letrametliylthiuram (lisulfldo (TMTD)(for com- 3 4 purison purposes) Control (untreated) 5 EXAMPLE 2Following the procedure described in Example 1, the active ingredientswere dissolved in acetone and distributed in a malt nutrient agar. Theagar was" again poured into Petri dishes having a diameter of 5 cm andeach dish was centrally inoculated with mycelium flakes of Coniophoracerebella. The dishes were incubated at 25C and the extent of thedevelopment of the Coniophora ccrebella percentage active ingredient inthe agar Active ingredient 0.025 0.01

(3H C O 8- CH Tetramethylthiurom disulfide (TMTD) (for comparisonpurposes) 2 Control (untreated) t. 5

EXAMPLE 3 I The procedure was that adopted in Example 1. The fungusemployed for the purposes of the experiment was Sclerotium rolfsii. Theextent of the development of the fungus colony was ascertained after 4days.

The figures in the table have the following meanings:

no fungus growth Sclerotium rolfaii percentage active lngrelo dient inthe agar O 0 Cl -Cos-cH CH; o 0 Cl COSC2H CH3 -COOCH2-$H -COOC3H7COO-CH3 COS H O 1 r-NO2 -COSCH3 0 0 C1 K so COSCH3 -COSCII3 O2N- COS-CH3Totramethylthiuram disulfide (TMTD) (for comparison purposes) 2 3Control (untreated) 5 EXAMPLE 4 The active ingredients, in amounts of 20and 40 percent by weight, were thoroughly triturated with talc. 0.01part by weight of spores of wheat bunt (TiIIetia tritici) was uniformlydistributed in 0.2 part by weight portions of the active ingredient/talcmixtures and the resultant mixtures were dusted onto 10 parts by weightof soaked and drained soil in Petri dishes having va diameter of 5 cm.Thedishes were then kept in a refrigerator at 10 to l2C. After 10 daysthe spores in the control dish (spore/talc mixture) had germinated;

enabling the effectiveness of the agents to be determined according tothe following table:

+H- strong germination; corresponding to the control -H- markedlyreduced germination considerably reduced germination, only occuringsporadically 0 total inhibition of germination Tilletia triticipercentage active ingredient in the mixture Activo ingredient 2O 40 0 0&

new, mm 2isopropyl-S'-methylphenyl-2-methylbenzoate ISO bu tylo-methylbenzoate mlXtulO methyl-Z-mtrobenzoate Activuingl'uilient j 403-methylphenyl-2-chlorobenzoate 5 thioisopropyl-2-nitrobenzoate 0 umpropyl-Z-mtrobenzoate thiomethyl-2-chloro-5-nitrobenzoatephenyI-Z-methylbenzoate thiophenyl-2-chlorobenzoateisobutyl-2-chlorobenzoate isobutyl-Z-nitrobenzoate -COS-CH3thioethyl-2-chlorobenzoate thloisopropyl2-chlorobenzoate 0 0methyl-2-methylbenzoate thiomethyl-2-methylbenzoatethiomethyl-2-chlorobenzoate thiomethyl-2-nitrobenzoate CH 0 0ethyl-Z-methylbenzoate propyl-2-methylbenzoate 0 Qthioethyl-Z-chlorobenzoate isopropyI-Z-methylbenzoate iallyl-2-methylbenzoate "1 0 U thiododecyl-2-chlorobenzoate lthiooctyl-2-nitrobenzoate 4:11;. 2', 3', 4', 5,6-pentachlorophenyl-2-nitrobenzoate U 4'-isooctylphenyl-2-methylbenzoatecos-om methylZ-chlorobenzoate thiododecyl-Z-methylbenzoate 0 0 3propyl-2-chlorobenzoate 0 benzyl-2-methylbenzoate2'-methylphenyl-Z-methylbenzoate and 2'methylphenyl-Z-chlorobenzoate 0 02. A process for controlling fungi which comprises applying to plants,seeds or seedlings an effective, fungitoxlc amount ofa compound havingthe formula (3H3 o 0 CI-I.

1 COOCHz Control (untreated) (spore/talc mixturc) s... t. process forcontrolling fling] whlch cqmpnses applying to plants, seeds or seedlingsan effective, fungitoxic amount of a compound having the formula Weclaim: I 7 C 1. A process for controlling fungi which comprises lapplying to plants, seeds, or seedlings an effective, Q-COOCH:

fungi-toxic amount of a compound selected from the group consisting ofthiomethyl 2,3-dimethylbenzoate thiooctyl o-chlorobenzoate

2. A process for controlling fungi which comprises applying to plants,seeds or seedlings an effective, fungitoxic amount of a compound havingthe formula
 3. A process for controlling fungi which comprises applyingto plants, seeds or seedlings an effective, fungitoxic amount of acompound having the formula